Polymer composite photonic crystal coatings

Patent metadata

Field	Value
Publication number	US-12091570-B2
Application number	US-202117390238-A
Country	US
Kind code	B2
Filing date	Jul 30, 2021
Priority date	Jan 30, 2019
Publication date	Sep 17, 2024
Grant date	Sep 17, 2024

Abstract

Polymer composite photonic crystal materials are disclosed as coatings which have high reflection (>30%) in a specific range of the electromagnetic spectrum, such as ultraviolet (<400 nm), visible (Vis, 400 nm-700 nm), or near-infrared radiation range (NIR, 700-2000 nm), and relatively low reflection (<20% reflection) in a second, different range of the electromagnetic spectrum. Surprisingly, it was found that through a formulation and additives approach, the optical properties of polymer composite photonic crystal films can be selectively modified from a variety of different coating methods, including spray deposition.

First claim

What is claimed is:

1. A photonic crystal composition comprising brush block copolymer (BBCP) of Formula IA or Formula IB:

and optionally a pigment;
wherein
R x is —(C 2 -C 6 )alkyl-OC(═O)G 1 , wherein G 1 comprises polyacrylate, polymethacrylate or polylactic acid; or
—(C 1 -C 8 )alkyl-G 2 -G 3 , wherein G 2 is —C(═O)O— or a nitrogen heterocycle and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid;
R y is —(C 2 -C 6 )alkyl-OC(═O)G 1 , wherein G 1 comprises polyacrylate, polymethacrylate or polylactic acid; or
—(C 1 -C 8 )alkyl-G 2 -G 3 , wherein G 2 is —C(═O)O— or a nitrogen heterocycle and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid;
R 1 is unbranched alkyl;
R 2 is branched alkyl;
each G is each independently CH 2 or C=0;
each J 1 is independently CH 2 , C═O, or O;
each J 2 is independently CH 2 , C═O, or O;
each Q is independently alkyl, cycloalkyl, heterocycloalkyl, carbonyl, silyl, aryl, or heteroaryl;
a and b are each independently 0 to 1000; and
x and y are each independently 1 to 1000;
wherein blocks a, b, x and y are in any order, a ratio of x:a is 1:0 to 1:3, and a ratio of y:b is 1:0 to 1:3.

2. The composition of claim 1 , wherein composition comprises a pigment and the pigment is an acid dye, basic dye, azo dye, acridine dye, rylene dye, sulfur dye, pH indicator, food dye, fluorescent brightener, anthraquinone dye, arylmethane dye, triarylmethane dye, phthalocyanine dye, quinone-imine dye, azin dye, indophenol dye, oxazin dye, oxazone dye, thiazine dye, thiazole dye, safranin dye, xanthene dye, perylene diimide dye, rhodamine dye, or a combination thereof.

3. The composition of claim 2 , wherein the pigment is acridine, bromothymol, carmine, Eosin Y, Guaiazulene, perylene, or a combination thereof.

4. The composition of claim 1 , wherein a and b are each independently 1 to 300, or x and y are each independently 1 to 300.

5. The composition of claim 1 , wherein the ratio of x:a is 1:0.5 to 1:1.

6. The composition of claim 1 , wherein the ratio of y:b is 1:0.5 to 1:1.

7. The composition of claim 1 , wherein a weight percent of the BBCP is 25% to 99.9% and the weight percent of the pigment is 0.1% to 10%.

8. The composition of claim 1 , wherein the composition further comprises a metal oxide, a polymer additive, or a combination thereof.

9. The composition of claim 1 , wherein the composition further comprises zirconium dioxide nanocrystals.

10. The composition of claim 1 , wherein the BBCP of Formula IA is a BBCP of Formula IC or Formula II:

wherein
R 3 and R 4 are each independently H or unbranched or branched—(C 1 -C 6 )alkyl; and
m and n are each independently 1 to 100.

11. The composition of claim 10 , wherein m and n are each independently 10 to 50.

12. The composition of claim 1 , wherein the BBCP of Formula IA is a BBCP of Formula III:

wherein
R 5 is H or unbranched or branched—(C 1 -C 6 )alkyl; and
q and t are each independently 1 to 100.

13. A method of modulating an electromagnetic radiation reflectance, absorbance and transmission profile of a substrate comprising coating a substrate with a film of a photonic crystal composition,
wherein the photonic crystal composition comprises brush block copolymer (BBCP) of Formula IA or Formula IB:

and a pigment;
wherein
R x is —(C 2 -C 6 )alkyl-OC(═O)G 1 , wherein G 1 comprises polyacrylate, polymethacrylate or polylactic acid; or
—(C 1 -C 8 )alkyl-G 2 -G 3 , wherein G 2 is —C(═O)O— or a nitrogen heterocycle and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid;
R y is —(C 2 -C 6 )alkyl-OC(═O)G 1 , wherein G 1 comprises polyacrylate, polymethacrylate or polylactic acid; or
—(C 1 -C 8 )alkyl-G 2 -G 3 , wherein G 2 is —C(═O)O— or a nitrogen heterocycle and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid;
R 1 is unbranched alkyl;
R 2 is branched alkyl;
each G is each independently CH 2 or C=0;
each J 1 is independently CH 2 , C═O, or O;
each J 2 is independently CH 2 , C═O, or O;
each Q is independently alkyl, cycloalkyl, heterocycloalkyl, carbonyl, silyl, aryl, or heteroaryl;
a and b are each independently 0 to 1000; and
x and y are each independently 1 to 1000;
wherein blocks a, b, x and y are in any order, a ratio of x:a is 1:0 to 1:3, and a ratio of y:b is 1:0 to 1:3;
wherein the pigment is an acid dye, basic dye, azo dye, acridine dye, rylene dye, sulfur dye, pH indicator, food dye, fluorescent brightener, anthraquinone dye, arylmethane dye, triarylmethane dye, phthalocyanine dye, quinone-imine dye, azin dye, indophenol dye, oxazin dye, oxazone dye, thiazine dye, thiazole dye, safranin dye, xanthene dye, perylene diimide dye, rhodamine dye, or a combination thereof; and
wherein the pigment in the photonic crystal composition modulates the reflectance, absorbance and transmission profile of the substrate and at least 5% more electromagnetic radiation is reflected by the coated substrate than for a corresponding uncoated substrate.

14. The method of claim 13 , wherein the film has an optical thickness f-ratio of 0.25 to 0.55.

15. The method of claim 13 , wherein the reflectance, absorbance and transmission profile of the substrate comprises reflected electromagnetic radiation at wavelengths of 280 nanometers to 400 nanometers; or
the reflectance, absorbance and transmission profile of the substrate comprises reflected electromagnetic radiation at wavelengths of 400 nanometers to 700 nanometers; or
the reflectance, absorbance and transmission profile of the substrate comprises reflected electromagnetic radiation at wavelengths of 700 nanometers to 1600 nanometers.

16. A method for forming a photonic coating comprising:
a) combining a solvent, a pigment, and a brush block copolymer (BBCP) to form a mixture, wherein BBCP is a BBCP of Formula IC:

wherein
R x is —(C 2 -C 6 )alkyl-OC(═O)G 1 , wherein G 1 comprises polyacrylate, polymethacrylate or polylactic acid; or
—(C 1 -C 5 )alkyl-G 2 -G 3 , wherein G 2 is —C(═O)O— or a nitrogen heterocycle and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid;
R y is —(C 2 -C 6 )alkyl-OC(═O)G 1 , wherein G 1 comprises polyacrylate, polymethacrylate or polylactic acid; or
—(C 1 -C 5 )alkyl-G 2 -G 3 , wherein G 2 is —C(═O)O— or a nitrogen heterocycle and G 3 comprises polystyrene, polyacrylate, polydimethylsiloxane, polyether, polymethacrylate, or polylactic acid;
R 1 is unbranched alkyl;
R 2 is branched alkyl;
a and b are each independently 0 to 1000; and
x and y are each independently 1 to 1000;
wherein a ratio of x:a is 1:0 to 1:3 and a ratio of y:b is 1:0 to 1:3;
b) applying a layer of the mixture to a substrate; and
c) drying the layer to form a film;

wherein the film forms the photonic coating on the substrate.

Assignees

• Univ Colorado State Res Found

Inventors

• Ryan Matthew David
• Miyake Garret
• Pearson Ryan Michael

Classifications

• G02B1/11

  Anti-reflection coatings · CPC title

• C09D5/32

  Radiation-absorbing paints {(protection against X-, gamma- or corpuscular radiation G21F)} · CPC title

• C09D5/004

  Reflecting paints; Signal paints · CPC title

• C08K2003/2244

  of zirconium · CPC title

• C08K13/02

  Organic and inorganic ingredients · CPC title